A deep understanding of thermodynamics is essential to success in a wide range of chemical and biochemical engineering applications. In this book, two leading experts and long-time instructors thoroughly explain the subject, taking the molecular perspective that working engineers require (and competitive books often avoid). This new and renamed Second Edition contains extensive new coverage of today's fast-growing biochemical engineering applications, notably biomass conversion to fuels and chemicals. It also presents many new MATLAB examples and tools to complement its previous usage of Excel and other software. New and updated coverage includes: Integrated discussions of biological thermodynamics throughout Clear learning objectives and outcomes for each chapter, provided as a web supplement More examples focusing on the First and Second Laws of thermodynamics and fluid phase equilibria in mixtures A new overview of mixture modeling concepts Reorganized, enhanced coverage of van der Waals and local composition models A brand-new chapter on molecular simulations Expanded coverage of stability theory Updated online supplements and new online teaching tools, including ConceptTesting

*Preface xvii* *About the Authors xix*

*Glossary xxi*

*Notation xxv*

**Unit I: First and Second Laws 1**

**Chapter 1: Basic Concepts 3 **

1.1 Introduction 5

1.2 The Molecular Nature of Energy, Temperature, and Pressure 6

1.3 The Molecular Nature of Entropy 15

1.4 Basic Concepts 15

1.5 Real Fluids and Tabulated Properties 22

1.6 Summary 33

1.7 Practice Problems 34

1.8 Homework Problems 35

**Chapter 2: The Energy Balance 39**

2.1 Expansion/Contraction Work 40

2.2 Shaft Work 41

2.3 Work Associated with Flow 41

2.4 Lost Work versus Reversibility 42

2.5 Heat Flow 46

2.6 Path Properties and State Properties 46

2.7 The Closed-System Energy Balance 48

2.8 The Open-System, Steady-State Balance 51

2.9 The Complete Energy Balance 56

2.10 Internal Energy, Enthalpy, and Heat Capacities 57

2.11 Reference States 63

2.12 Kinetic and Potential Energy 66

2.13 Energy Balances for Process Equipment 68

2.14 Strategies for Solving Process Thermodynamics Problems 74

2.15 Closed and Steady-State Open Systems 75

2.16 Unsteady-State Open Systems 80

2.17 Details of Terms in the Energy Balance 85

2.18 Summary 86

2.19 Practice Problems 88

2.20 Homework Problems 90

**Chapter 3: Energy Balances for Composite Systems 95**

3.1 Heat Engines and Heat Pumps — The Carnot Cycle 96

3.2 Distillation Columns 101

3.3 Introduction to Mixture Properties 105

3.4 Ideal Gas Mixture Properties 106

3.5 Mixture Properties for Ideal Solutions 106

3.6 Energy Balance for Reacting Systems 109

3.7 Reactions in Biological Systems 119

3.8 Summary 121

3.9 Practice Problems 122

3.10 Homework Problems 122

**Chapter 4: Entropy 129**

4.1 The Concept of Entropy 130

4.2 The Microscopic View of Entropy 132

4.3 The Macroscopic View of Entropy 142

4.4 The Entropy Balance 153

4.5 Internal Reversibility 158

4.6 Entropy Balances for Process Equipment 159

4.7 Turbine, Compressor, and Pump Efficiency 164

4.8 Visualizing Energy and Entropy Changes 165

4.9 Turbine Calculations 166

4.10 Pumps and Compressors 173

4.11 Strategies for Applying the Entropy Balance 175

4.12 Optimum Work and Heat Transfer 177

4.13 The Irreversibility of Biological Life 181

4.14 Unsteady-State Open Systems 182

4.15 The Entropy Balance in Brief 185

4.16 Summary 185

4.17 Practice Problems 187

4.18 Homework Problems 189

**Chapter 5: Thermodynamics Of Processes 199**

5.1 The Carnot Steam Cycle 199

5.2 The Rankine Cycle 200

5.3 Rankine Modifications 203

5.4 Refrigeration 208

5.5 Liquefaction 212

5.6 Engines 214

5.7 Fluid Flow 214

5.8 Problem-Solving Strategies 214

5.9 Summary 215

5.10 Practice Problems 215

5.11 Homework Problems 216

**Unit II: Generalized Analysis of Fluid Properties 223**

**Chapter 6: Classical Thermodynamics – Generalizations For Any Fluid 225**

6.1 The Fundamental Property Relation 226

6.2 Derivative Relations 229

6.3 Advanced Topics 244

6.4 Summary 247

6.5 Practice Problems 248

6.6 Homework Problems 248

**Chapter 7: Engineering Equations of State for PVT Properties 251**

7.1 Experimental Measurements 252

7.2 Three-Parameter Corresponding States 253

7.3 Generalized Compressibility Factor Charts 256

7.4 The Virial Equation of State 258

7.5 Cubic Equations of State 260

7.6 Solving the Cubic Equation of State for *Z* 263

7.7 Implications of Real Fluid Behavior 269

7.8 Matching the Critical Point 270

7.9 The Molecular Basis of Equations of State: Concepts and Notation 271

7.10 The Molecular Basis of Equations of State: Molecular Simulation 276

7.11 The Molecular Basis of Equations of State: Analytical Theories 282

7.12 Summary 289

7.13 Practice Problems 290

7.14 Homework Problems 291

**Chapter 8: Departure Functions 301**

8.1 The Departure Function Pathway 302

8.2 Internal Energy Departure Function 304

8.3 Entropy Departure Function 307

8.4 Other Departure Functions 308

8.5 Summary of Density-Dependent Formulas 308

8.6 Pressure-Dependent Formulas 309

8.7 Implementation of Departure Formulas310

8.8 Reference States 318

8.9 Generalized Charts for the Enthalpy Departure 323

8.10 Summary 323

8.11 Practice Problems 325

8.12 Homework Problems326

**Chapter 9: Phase Equilibrium in a Pure Fluid 335**

9.1 Criteria for Phase Equilibrium 336

9.2 The Clausius-Clapeyron Equation 337

9.3 Shortcut Estimation of Saturation Properties 339

9.4 Changes in Gibbs Energy with Pressure 342

9.5 Fugacity and Fugacity Coefficient 344

9.6 Fugacity Criteria for Phase Equilibria 346

9.7 Calculation of Fugacity (Gases) 347

9.8 Calculation of Fugacity (Liquids) 348

9.9 Calculation of Fugacity (Solids) 353

9.10 Saturation Conditions from an Equation of State 353

9.11 Stable Roots and Saturation Conditions 359

9.12 Temperature Effects on *G* and *f* 361

9.13 Summary 361

9.14 Practice Problems 362

9.15 Homework Problems 363

**Unit III: Fluid Phase Equilibria in Mixtures 367**

**Chapter 10: Introduction to Multicomponent Systems 369**

10.1 Introduction to Phase Diagrams 370

10.2 Vapor-Liquid Equilibrium (VLE) Calculations 372

10.3 Binary VLE Using Raoult’s Law 374

10.4 Multicomponent VLE Raoult’s Law Calculations 381

10.5 Emissions and Safety 386

10.6 Relating VLE to Distillation 390

10.7 Nonideal Systems 393

10.8 Concepts for Generalized Phase Equilibria 397

10.9 Mixture Properties for Ideal Gases 401

10.10 Mixture Properties for Ideal Solutions 403

10.11 The Ideal Solution Approximation and Raoult’s Law 404

10.12 Activity Coefficient and Fugacity Coefficient Approaches 405

10.13 Summary 405

10.14 Practice Problems 407

10.15 Homework Problems 407

**Chapter 11: An Introduction To Activity Models 411**

11.1 Modified Raoult’s Law and Excess Gibbs Energy 412

11.2 Calculations Using Activity Coefficients 416

11.3 Deriving Modified Raoult’s Law 423

11.4 Excess Properties 426

11.5 Modified Raoult’s Law and Excess Gibbs Energy 427

11.6 Redlich-Kister and the Two-Parameter Margules Models 429

11.7 Activity Coefficients at Special Compositions 432

11.8 Preliminary Indications of VLLE 434

11.9 Fitting Activity Models to Multiple Data 435

11.10 Relations for Partial Molar Properties 439

11.11 Distillation and Relative Volatility of Nonideal Solutions 442

11.12 Lewis-Randall Rule and Henry’s Law 443

11.13 Osmotic Pressure 449

11.14 Summary 454

11.15 Practice Problems 455

11.16 Homework Problems 455

**Chapter 12: van der Waals Activity Models 465**

12.1 The van der Waals Perspective for Mixtures 466

12.2 The van Laar Model 469

12.3 Scatchard-Hildebrand Theory 471

12.4 The Flory-Huggins Model 474

12.5 MOSCED and SSCED Theories 479

12.6 Molecular Perspective and VLE Predictions 483

12.7 Multicomponent Extensions of van der Waals’ Models 486

12.8 Flory-Huggins and van der Waals Theories 491

12.9 Summary 492

12.10 Practice Problems 494

12.11 Homework Problems 495

**Chapter 13: Local Composition Activity Models 499**

13.1 Local Composition Theory 501

13.2 Wilson’s Equation 505

13.3 NRTL 508

13.4 UNIQUAC 509

13.5 UNIFAC 514

13.6 COSMO-RS Methods 520

13.7 The Molecular Basis of Solution Models 526

13.8 Summary 532

13.9 Important Equations 533

13.10 Practice Problems 533

13.11 Homework Problems 534

**Chapter 14: Liquid-Liquid and Solid-Liquid Phase Equilibria 539**

14.1 The Onset of Liquid-Liquid Instability 539

14.2 Stability and Excess Gibbs Energy 542

14.3 Binary LLE by Graphing the Gibbs Energy of Mixing 543

14.4 LLE Using Activities 545

14.5 VLLE with Immiscible Components 548

14.6 Binary Phase Diagrams 549

14.7 Plotting Ternary LLE Data 551

14.8 Critical Points in Binary Liquid Mixtures 552

14.9 Numerical Procedures for Binary, Ternary LLE 556

14.10 Solid-Liquid Equilibria 556

14.11 Summary 569

14.12 Practice Problems 570

14.13 Homework Problems 570

**Chapter 15: Phase Equilibria in Mixtures by an Equation of State 579 **

15.1 Mixing Rules for Equations of State 580

15.2 Fugacity and Chemical Potential from an EOS 582

15.3 Differentiation of Mixing Rules 588

15.4 VLE Calculations by an Equation of State 594

15.5 Strategies for Applying VLE Routines 603

15.6 Summary 603

15.7 Practice Problems 604

15.8 Homework Problems 606

**Chapter 16: Advanced Phase Diagrams 613**

16.1 Phase Behavior Sections of 3D Objects 613

16.2 Classification of Binary Phase Behavior 617

16.3 Residue Curves 630

16.4 Practice Problems 636

16.5 Homework Problems 636

**Unit IV: Reaction Equilibria 639**

**Chapter 17: Reaction Equilibria 641**

17.1 Introduction 642

17.2 Reaction Equilibrium Constraint 644

17.3 The Equilibrium Constant 646

17.4 The Standard State Gibbs Energy of Reaction 647

17.5 Effects of Pressure, Inerts, and Feed Ratios 649

17.6 Determining the Spontaneity of Reactions 652

17.7 Temperature Dependence of *K*_{a} 652

17.8 Shortcut Estimation of Temperature Effects 655

17.9 Visualizing Multiple Equilibrium Constants 656

17.10 Solving Equilibria for Multiple Reactions 658

17.11 Driving Reactions by Chemical Coupling 662

17.12 Energy Balances for Reactions 664

17.13 Liquid Components in Reactions 667

17.14 Solid Components in Reactions 669

17.15 Rate Perspectives in Reaction Equilibria 671

17.16 Entropy Generation via Reactions 672

17.17 Gibbs Minimization 673

17.18 Reaction Modeling with Limited Data 677

17.19 Simultaneous Reaction and VLE 677

17.20 Summary 683

17.21 Practice Problems 684

17.22 Homework Problems 686

**Chapter 18: Electrolyte Solutions 693**

18.1 Introduction to Electrolyte Solutions 693

18.2 Colligative Properties 695

18.3 Speciation and the Dissociation Constant 697

18.4 Concentration Scales and Standard States 699

18.5 The Definition of pH 701

18.6 Thermodynamic Network for Electrolyte Equilibria 702

18.7 Perspectives on Speciation 703

18.8 Acids and Bases 704

18.9 Sillèn Diagram Solution Method712

18.10 Applications 723

18.11 Redox Reactions 727

18.12 Biological Reactions 731

18.13 Nonideal Electrolyte Solutions: Background 739

18.14 Overview of Model Development 740

18.15 The Extended Debye-Hückel Activity Model 742

18.16 Gibbs Energies for Electrolytes 743

18.17 Transformed Biological Gibbs Energies and Apparent Equilibrium Constants 745

18.18 Coupled Multireaction and Phase Equilibria 749

18.19 Mean Ionic Activity Coefficients 753

18.20 Extending Activity Calculations to High Concentrations 755

18.21 Summary 755

18.22 Supplement 1: Interconversion of Concentration Scales 757

18.23 Supplement 2: Relation of Apparent Chemical Potential to Species Potentials 758

18.24 Supplement 3: Standard States 759

18.25 Supplement 4: Conversion of Equilibrium Constants 760

18.26 Practice Problems 761

18.27 Homework Problems 761

**Chapter 19: Molecular Association and Solvation 767**

19.1 Introducing the Chemical Contribution 768

19.2 Equilibrium Criteria 772

19.3 Balance Equations for Binary Systems 775

19.4 Ideal Chemical Theory for Binary Systems 776

19.5 Chemical-Physical Theory 779

19.6 Wertheim’s Theory for Complex Mixtures 782

19.7 Mass Balances for Chain Association 792

19.8 The Chemical Contribution to the Fugacity Coefficient and Compressibility Factor 793

19.9 Wertheim’s Theory of Polymerization 795

19.10 Statistical Associating Fluid Theory (The SAFT Model) 799

19.11 Fitting the Constants for an Associating Equation of State 802

19.12 Summary 804

19.13 Practice Problems 806

19.14 Homework Problems 806

**Appendix A: Summary of Computer Programs 811**

A.1 Programs for Pure Component Properties 811

A.2 Programs for Mixture Phase Equilibria 812

A.3 Reaction Equilibria 813

A.4 Notes on Excel Spreadsheets 813

A.5 Notes on MATLAB 814

A.6 Disclaimer 815

**Appendix B: Mathematics 817**

B.1 Important Relations 817

B.2 Solutions to Cubic Equations 822

B.3 The Dirac Delta Function 825

**Appendix C: Strategies for Solving VLE Problems 831**

C.1 Modified Raoult’s Law Methods 832

C.2 EOS Methods 835

C.3 Activity Coefficient (Gamma-Phi) Methods 838

**Appendix D: Models for Process Simulators 839**

D.1 Overview 839

D.2 Equations of State 839

D.3 Solution Models 840

D.4 Hybrid Models 840

D.5 Recommended Decision Tree 841

**Appendix E: Themodynamic Properties 843**

E.1 Thermochemical Data 843

E.2 Latent Heats 846

E.3 Antoine Constants 847

E.4 Henry’s Constant with Water as Solvent 847

E.5 Dielectric Constant for Water 848

E.6 Dissociation Constants of Polyprotic Acids 849

E.7 Standard Reduction Potentials 849

E.8 Biochemical Data 852

E.9 Properties of Water 854

E.10 Pressure-Enthalpy Diagram for Methane 865

E.11 Pressure-Enthalpy Diagram for Propane 866

E.12 Pressure-Enthalpy Diagram for R134a (1,1,1,2-Tetraflouroethane) 867

*Index 869*